Kinetic studies of the reactions CH2I2 + HI⇄CH3I + I2 and 2 CH3I⇄CH4 + CH2I2 the heat of formation of the iodomethyl radical

The rate of the reaction CH₂I₂ + HI ? CH₃I + I₂ has been followed spectrophotometrically from 201.0 to 311.2°. The rate constant for the reaction fits the equation, log (k₁/M^?1 sec^?1) = 11.45 ± 0.18 - (15.11 ± 0.44)/θ. This value, combined with the assumption that E₂ = 0 ± 1 kcal/mole, leads to ΔH (CH₂I, g) = 55.0 ± 1.6 kcal/mole and DH (H? CH₂I) = 103.8 ± 1.6 kcal/mole. The kinetics of the disproportionation, 2 CH₃I ? CH₄ + CH₂I₂ were studied at 331° and are compatible with the above values.     

Very-low-pressure pyrolysis of nitroso- and pentafluoronitrosobenzene C?NO bond dissociation energies

The high-pressure absolute rate constants for the decomposition of nitrosobenzene and pentafluoronitrosobenzene were determined using the very-low-pressure pyrolysis (VLPP) technique. Bond dissociation energies of DH⁰(C₆H₅? NO) = 51.5 ± 1 kcal/mole and DH⁰ (C₆F₅? NO) = 50.5 ± 1 kcal/mole could be deduced if the radical combination rate constant is set at log k_r(M^?1·sec^?1) = 10.0 ± 0.5 for both systems and the activation energy for combination is taken as 0 kcal/mole at 298°K. δH_f⁰(C₆H₅NO), δH_f⁰(C₆F₅NO), and δH_f⁰(C₆F₅) could be estimated from our kinetic data and group additivity. The values are 48.1 ± 1, –160 ± 2, and – 130.9 ± 2 kcal/mole, respectively. C–X bond dissociation energies of several perfluorinated phenyl compounds, DH⁰(C₆F₅–X), were obtained from the reported values of δH_f⁰(C₆F₅X) and our estimated δH_f⁰(C₆F₅) [X = H, CH₃, NO, Cl, F, CF₃, I, and OH].     

Joys and pitfalls of fermi surface mapping in Bi(2)Sr(2)CaCu(2)O(8+delta) using angle resolved photoemission

On the basis of angle-scanned photoemission data recorded using unpolarized radiation, with high (E,k) resolution, and an extremely dense sampling of k space, we resolve the current controversy regarding the normal state Fermi surface (FS) in Bi(2)Sr(2)CaCu(2)O(8+delta). The true picture is simple, self-consistent, and robust: the FS is holelike, with the form of rounded tubes centered on the corners of the Brillouin zone. Two further types of features are also clearly observed: shadow FSs, which are most likely to be due to short range antiferromagnetic spin correlations, and diffraction replicas of the main FS caused by passage of the photoelectrons through the modulated Bi-O planes.     

Evaluation of data for atmospheric models: Master Equation/RRKM calculations on the combination reaction ClO + NO2 → ClONO2, a recurring issue

Experimental data for the title reaction have been modeled using Master Equation/RRKM methods based on the Multiwell suite of programs. The starting point for the exercise was the empirical fitting provided by the NASA and IUPAC data evaluation panels, which represent the data in the experimental pressure ranges rather well. Despite the availability of quite reliable parameters for these calculations (molecular vibrational frequencies and a value of the bond dissociation energy of ClONO₂, DH₂₉₈(ClONO₂) = 26.5 kcal mol^?1, corresponding to ΔH₀⁰ = 25.35 kcal mol^?1 at 0 K) and use of RRKM/Master Equation methods, fitting calculations to the reported data was anything but straightforward. Using these molecular parameters resulted in a discrepancy between the calculations and the database of rate constants of a factor of ca 4 at, or close to, the low‐pressure limit. © 2009 Wiley Periodicals, Inc. Int J Chem Kinet 41: 573–581, 2009     

High‐temperature shock tube study of the reactions CH3 + OH → products and CH3OH + Ar → products

The reaction between methyl and hydroxyl radicals has been studied in reflected shock wave experiments using narrow‐linewidth OH laser absorption. OH radicals were generated by the rapid thermal decomposition of tert‐butyl hydroperoxide. Two different species were used as CH₃ radical precursors, azomethane and methyl iodide. The overall rate coefficient of the CH₃ + OH reaction was determined in the temperature range 1081–1426 K under conditions of chemical isolation. The experimental data are in good agreement with a recent theoretical study of the reaction. The decomposition of methanol to methyl and OH radicals was also investigated behind reflected shock waves. The current measurements are in good agreement with a recent experimental study and a master equation simulation. © 2008 Wiley Periodicals, Inc. 40: 488–495, 2008     

Multilayer Film Fabrication Using Flow Injection Coupled with Electrochemical Deposition

A simple method is proposed for the electrodeposition of multilayers using a modified closed flow injection system. The apparatus incorporates flowing streams of electrolyte through a closed atmosphere flow cell for deposition of multilayers. Computer and software control is used to alternate the flow of electrolyte and control the alternating current or potential of the electrochemical cell. Electrodeposition of metallic multilayers of nickel/iron, iron/copper, cobalt/copper, and nickel/copper were used to test the instrument design. X‐ray diffraction was used to verify the composition and orientation of the films and scanning electron microscopy was used to examine the morphology of the deposited films. Advantages are discussed for using this type of instrumental setup for multilayer fabrication.     

Problems of non-uniqueness when interpreting the effect of fluid inertia on the complex viscosity function

A theoretical investigation is carried out into the interpretation of the effect of fluid inertia on the complex viscosity function as measured on a controlled stress rheometer. The problem of non-unique solutions to the governing equations is considered for the parallel plate geometry. The locations of these solutions are investigated by considering the critical points of the complex mapping associated with the linear viscoelastic equations of motion. It is shown that these critical points play an important role in determining where convergence problems are likely to occur when applying numerical methods of solution to the governing equations. Analytical approximations based on a series expansion about a critical point are developed as an alternative approach to a numerical solution in the neighbourhood of a critical point. In order to verify the theoretical predictions a numerical simulation of the behaviour of a single element Maxwell fluid on a controlled stress rheometer is carried out for a parallel plate geometry. Received: 27 July 1998 Accepted: 9 April 1999